Process of refining petroleum oil



J. F. WAIT Filed May 24, 19.33

` A1N VENTVOR PROCESS OF REFINING PETROLEUM OIL De@ s, 1936.

Patented Dec. 83

UNITED STATES I PATENT oFF1cE raocEss oF REFINING PETROLEUM olL l JustinF. Wait, newyork, N. Y. Application May 24, 193s, serial No. 672,572

7 Claims.

and it is further related to co-pending applications including Ser. Nos. 671,187 tiled May 15, 1933; 671,616 led May 18, 1933, and 671,895 filed May 19, 1933. I

Among the light active metals which may be applied for the treatment of oil are those with one unpaired electron including sodium, potassium and aluminum. Such metals may be utilized inassociation with compounds of such metals my preference being `for hydroxides and chlorides appropriately mixed to give desired activity and fluidity. The temperature of application is preierably between about 250 C. and 500 C. wherefor I take advantage of the high degree of activity of the petroleum as well as the' metal. 'Ihe metal may be at the same temperature as vapors of oil being treated or at a higher temperature. A portion of the oil may be treated in the liquid)` phase.

Although it has been suggested that alkali metals and alkaline earth metals might be used for treating oil, the proposed application appears to have been limited to 'the removal of sulfur or sulfur compounds from gasoline.- The suggested and described methods of application. fail to provide for conditions which are necessary to the realization of a practical eiect and in particular they fail to recognize that extensive purification and molecular rearrangement of oil may bel promoted by application of such metals and compounds in proper manner. It has previously been.' considered desirable to use temperatures below about 200 C. and'in some instances room-or lowertemperatures. Proper contact has not been assured or'the method has been such as to pre- Avent continued use of a mass of metal or adequate recovery thereof. Compounds have not -been utilized with such metals and if at all in a wet condition. The metals, have not been applied to freshly` formed or' lfreshly treated I oil and vapors and their use has been limited to oils which have been altered considerably by storage.

By one phase of my invention appropriate portions of4 freshly treated and formed oils are con-l tacted with fused active metals and metallic coml pounds. Oil is cracked and the vapors of lighti gol. 196-35) cracked products are quickly treated by a molten lstream containing light active metal at between 200 7 C. and 500 C. while the heavy oil, residual to the vapors is separately treated and preferably at between about 200 C. and 350 C. Under 5 the conditions of the treatment molecular rearrangement'A takes place and impurities are removed with a resulting increase in stability and general improvement of properties of the oil.

Losses entailed in operation in other manners are 10l reduced or eliminated. I am thus 'able' to bene- `cially treat oils of all range.

Prior art has involvedftreatment yof old oil to such a slight extent that there has been no appreciable consumption of alkali metal whereas I control the conditions so that there is a decided consumption which under preferred conditions is considerably in excess of 1 lb. per bbl. and generally between about 5 and about 20 lbs. per bbl. of oil processed. Treatment with metal is combined with heating to cause cracking and rearrangement to the extent that each is required. Mild oxidation is applied before or between treatments With active molten mass to yield desired form and stability. Such oxidation is appreciably less than that previously applied and is extended to a degree that the metal treatl ment will yield high or highest stability.`

I'he particular mode of operation to be used is dependent upon the nature of the oil and the products desired. It cannot be predetermined and is established by testing oil to'be treated-by 'Y Y.

several combinations. In generalIestablish zones y of heating, zone of fractionation and zone of treatment with a vmolten mass. The oil in liquid 3,5'

or vapor form is' advanced and treated to in special manner and generally whilehoijl and Without cooling and lengthy storage which I have found to be generally detrimental. Prior applications disclose many steps usable in this invention and in- 40.

dicate results obtainable. By combining such stepsA it becomes possible to avoid or reduce deciencies obtained when thesteps arenot coordinated as indicated herein. v

The apparatus features andthe process feaures of my invention are illustrated in the drawing. 'A pump l supplies oil which may have been previously treated as by acid or extraction or .by appropriate combination of metal and compounds with or without mild oxidation to a pipe still 2 50 connected with a separating tank 3 serving sim- ,11 ilarly to a soaking tank. -A second such tank 4 is connected therewith by' means of.` line 5. A pump 6 and pipe still 1. may be usedto circulate and mix the contents oi' vessel l of which there 55 may be a number. This pipe still preferably adds but avraction of the amount of heat introduced by pipe still 2 and overcomes radiation and supplies heat for evaporation. The temperature within tank 4 is preferably a little above that in vessel 3. If several of vessels 4 are used the last is preferably within 100 F. of vessel 3. v'Ihe time of ow of liquid through these vessels is preferably less than about twenty minutes.

Separated vapors iiow through line 8 to contact tower 9 wherein there is circulated a molten massy containing a small amount of free alkali metal as for example less than one percent or so of sodium in a mixture of hydroxide such as sodium and potassium. The contact tower and method of operation may be as described in French Patents 756,203 and 755,875. 'I'he mass is circulated through an outside system which preferably contains means for both separation of impurities and activation by electrolysis. It may also contain means to heat the metal to a temperature above that of the vapors. The contact tower may be in multiple and one used for oxidation as by circulating a molten dinitro aromatic mass therethrough. Such mass may absorb impurities and be recovered as by evaporation.

Treated vapors may flow through line I0 to condenser II with outlet I2 to storage tank I3. Vessels 3 and 4 may be under one or several hundred pounds of pressure and the Aoil therewihin held at cracking temperature. Pipe still 2 is preferably operated so as to yield about 10% or 15% conversion into gasoline although a higher conversion may be attained in accordance with usual practice if desired. The pressure may be reduced in line 8 and/or lines I0 and I2 so that storage tank I3 is under about atmospheric pressure.

'I'he oil is owed through line I4 to pump I5 and may be mixed with other oil'or mild oxidant supplied through-line I 6. The pump discharges through line II to a battery of stills I8, I 9, 20 and ZI flowing in series therethrough. 'I'hese stills are representative of zones of heating and hence digestion. 'I'hese stills may be of the direct iired type and steam may be introduced as by means of lines 22 and 23. A small amount of air maybe introduced with the steam as at 22. Va-

. Dors are owed through line 24 to iractionating column 25 connected with condenser 2B, separator 21, back iiow line 28 and fon; .1rd ow line 29.

. which may be wet, through inlets 34 of intermediary still 20 of the series of stills I8, I9, 20, 2|, and 33 and oil vapors may likewise be added as to the inlet 35 of still 2|. Line 36 may be used to withdraw residual matter from time to time. Such matter is preferably cracked or otherwise worked as by flowing through line 31 with the residual mass from still 2I I prefer to hold temperature gradient between stills I8 and 2| so that the output of 32 will be of gasoline range.

Stills 38 and 39 are connected by line 40 and provided with lines 40 for introducing light vapors or gas which may be introduced and used to agitate and remove moisture; These Vstills further digest and associate portions of the oil. Condensers 4I and 42 may be used as indicated or they may be separated from the stills by a sl'iort'fractionating column for mild fractionation. Still 39 discharges to storage tank 4I supplying pump 42 feeding drum lm evaporator or the equivalent 43 (as shown in Ser. No. 670,742 filed May 6, 1933) with special fractionating column 44 which may beias shown in Ser. No. 461,941 led June 18, 1930. Condenser 45 is provided with back flow line 46 and forward :dow line 41. A separator above these lines (not shown) connects with high vacuurn means, the fractionating column being controlled so as to have no appreciable back pressure when heavy oils are reached or treated. Vessels 43, 44 and 45 may be in multiple. Alkali metal dispersed in 4oil may be introduced at the zone of 4I. Gases or light vapors may be introduced as indicated by line 4I so that it will be present during evaporation. Such gas may contain a mild oxidant. A contact tower may be provided between vessel 43 and 44 for treating with such metal. Back iiow may pass through line 4B to tank 4I or a portion or all withdrawn as through line 49: Experimentation is required to determine the most suitable method of operation of this and other parts of the system.

Flow of residual oil through soaking and separating tanks including 3 and 4 (several may be used) is such that successive portions are not appreciably mixed, there being a stage by stage reduction in the more volatile or less stable portions. 'Ihe temperature may be increased from stage to stage. Residual oil may be withdrawn as by means of lines 50 and 5I, preferably the latter. Oil from line 3l may if dry be introduced into pump I or into vessel 3 or another such as 4 if a multiplicity is used. In this manner reaction is promoted between the heavies of stills I8 to 2| and less stable portions thereof may be cracked. With some oils, I prefer to ow from line 34 into Vessel 52 or a similar vessel with agitator arms 54 turned by shaft 53. Residual oil from 5I is flowed into reactor 52 preferably in multiple arrangement. Mild oxidation may be applied to oil before or after introduction into one of these vessels. Alkali metal such as sodium is preferred for treatment of most oils. At a temperature between about 200 C. and 350 C. mild rearrangement -occurs and lights fractions are formed and removed as by line 55 and condenser 5B. When product from line 3l is treated alone' or with product from line 5I there is a considerable amount of such light fractions which may each about 10% or 20% of the total oil treated.

The treated heavy oil is passed through line 5l to storage vessel 58 with connection 59 to pump 60 discharging through line 6I to drum evaporator 62. Vapors are condensed in 63 and circulated liquid returned through line 64. I prefer to add suilcient metalso that roughly a quarter or a half a pound per barrel is present during evaporation. The consumption of sodium or like metal used in treating such oil may be about 5 lbs. to 10 lbs. of metal lper bbl. of oil, or higher if oxidation is applied.

In treating some oil I prefer to establish a second and connected zone of cracking. This is represented by pump 65, pipe still G6 and soaking tank 61 with vapor line 68 leading to contact ably under high pressure slightly greater than 'is that of contact tower 9. In general I prefer that tower 9 and vessels 3 and 4 should be at about a hundred or several hundred pounds pressure. Such pressure is preferably released on leaving condenser I l The vapors, gas or liquid added by means of line 68 may originate at points such as 29, 3|, 32, 39 and 56. It may contain a mild oxidant or small amounts of active metal. The outflow from 50 or 5| may be mixed with oil from one of the labove points and flowed through tanks 61 and 'I0 as indicated. Wax may be separated at one or more points, and it may.be-formed in applying my process to some oils. Separated wax may be treated to form oils of lubricating and lighter range. One or more of the illustrated steps may be omitted.

Each oil is treated in accordance with experimental findings and in view of the market requirements. I n general the degree and points of mild oxidation are governed by the degree of resistance to oxidation required of the final product and the amount of treatment with molten mass and the composition of the mass after oxidation is such as to attain a low gum or sludge value as required. The separation of heavy treated oil for lubricant is dependent uponthe requirements and may include contact filtration as for clarification or distillation by.mercury as previously described. I do.not limit my claims to the exact procedure illustrated.

1. In renng petroleum, the steps of flowing oil througha pipe still and applying heat to attain a cracking temperature, separating vapors from liquid, quickly flowing the vapors through a zone of contact with molten mass containing free active alkali, metal at between about 300 C. and 500 C., separately cracking oil by flow thereof through a second pipe still and a second separating zone and flowing the fixed gases with noteasily-condensed vapors thereof into the contact zone in contact with vapors from the first pipe still as they are being treated with the alkali metal, so promoting rearrangement of the vapors and combination of portions thereof, condensing vapors so treated and flowing them through a multiplicity -o'f stills with an oxidant to promote mild oxdationof increasing temperature, fractionating vapors therefrom, discharging oil residual to vapors fromcne still to a second zone of contact and treating the same thereat with alkali metal under reduced pressure at between 200 C. and 400 C. and volatilizing purified oil from the oil and treating agent spread in a thin film andunder substantial vacuum.

2. 'I'he process of refining petroleum oil which' comprises cracking oil, forming gasoline, separating gasoline and heavier vapors from residual oil, treating the residual oil with alkali metal at between about 200 C. and about 300 C., separating light oil so formed byrearrangement from the residual oil and separating purified lubricant from the metal and altered impurities, fractionating the vapors to form gasoline, treating heavier portions of the separated vapors with a mild oxidant to render unstable portions removable by treatment with alkali metal and applyingalkali metal y at between about 200 C. and 350 C. to remove oxidized unstable portions and separating lubri eating oil therefrom by evaporation under reduced pressure.

3. In treating oil of petroleum to form gasoline. a heavy lubricant and a light lubricant the process which comprises cracking the oil by applying heat, separating formed vapors and'treating them with alkali metal at between 200 C. and 500 C., treating residual oil of the cracking with a mild oxidant and then'with the molten mass containing alkali metal at between 200 C. and about 350 C., so forming light fractions and separating them, separating the heavy oil from the metal, and treating heavyportions of the treated vapors with a mild oxidant and subsequently with alkali metal at between about 200 C. and 350 C.

4. In refining petroleum, the process which comprises flowing oil through a pipe still and applying heat to attain` a cracking temperature, separating vapors from liquid, quickly flowing the vapors through ,a zone of contact with molten mass. containing free active alkali metal at between about 300 C. and 500 C., separately crackfixed gases .with not-easily-condensed vapors thereof into the contact zone in contact with vapors from the first pipe still asA they are being treated with the alkali metal, so promoting rearrangement of the vapors and combination of vportions thereof, condensing vapors so treated and aflowing them through a multiplicity of stills of increasing emperature, fractionating vapors therey from, di Y arging oil residual to vapors from one still to a second zone of contact and treating the same thereat with alkali metal under reduced pressureatbetween about 200 C. and about 400 .C. while forming light fractions from oil so f treated and evaporating and recovering improved oil of lubricating range therefrom.

5J. In refining petroleum, the process which comprises ,flowing oil through a pipe still and applying heat to attain a cracking temperature, separating vapors from liquid, quickly flowing the vapors through a zone of contact with molten mass containing free active alkali metal at between about 300 C.l and 500 C., separately cracking oil by flow thereof through a second pipe still and a second separating zon and flowing fixedgases with not `easily-condensed vapors thereof into the contact zone in contact with vapors from the .first pipe stillas they are being treated with the alkali metal, so promoting rearrangement of the vapors"and combination of portions thereof, condensing vapors so treated and flowing them through'a multiplicity of series-connected stills with an oxidant to promote mild oxidation of unstable portions and to render them removable 'by alkali metal while increasing the temperature and forming vapors therefrom while within the stills, discharging oil residual to vapors from one still to a second zone of contact and treating the same thereat with alkali metal under reduced pressure at between about 200 C. and about 400J C'. and volatilizing purified oil from the oil and treating agent spread in a thin film and under'substantial vacuum and fractionating and condensing improved and stabilized lubricating oil at the reduced pressure of evaporation.

6.' In refining petroleum, the process which comprises flowing oil'through a pipe still andapplying heat to attain a cracking temperature. separating vapors from liquid, `quiclf/:ly/iiovv'ing the vapors through a zone ,of contact with molten mass containing free active alkali'metal at between about 300 C. and 500 C., separately crackthe vapors and combination of portions thereof, Icondensing vapors so treated and flowing them through a multiplicity of stills with an oxidant to promote mild oxidation of unstable portions and to render them removable by alkali metal, increasing temperature of the oil owed through the stills and forming vapors therefrom. discharging oil residual to vapors from one still to a second zone of contact and treating the same thereat with alkali metal under reduced pressure at between about 200 C. and about 400 C. and volatilizing purified oil from the oil and treating agent under substantial vacuum and fractionating and condensing improved and stabilized lubricating oil at the reduced pressure of evaporation while maintaining the zones of cracking, separation and contact under substantial pressure.

7. The process which comprises owing oil through a cracking still to a zone of separation, treating the freshly formed vapors with a molten mass containing alkali metal at between about 300 C. and 500 C. to purify and improve the vapors, liquefying heavier portions of the so treated vapors and distilling the liquid at elevated temperatures for a substantial 'period while forming vapors and subsequently treating heavier portions o oil residual to the vapors with a mild oxidant to render unstable portions removable by application of alkali metal at elevated temperature and distilling the so oxidized oil under vacuum in the presence of alkali meta] at between about 200 C. and about 400 C. and separating and recovering portions of lubricating range.

- JUSTIN F. WAIT. 

